Isoalkylamine salts of organic sulphonic or carboxylic acids



Patented Apr. 6, 1943 ISOALKYLAMINE SALTS OF ORGANIC SUL- PHONIC OR OARBOXYLIO ACIDS Friedrich Nadler, Cologne-Mulheim, Richard Wegler, Leverkusen-Schlebusch, and Otto Bayer, Leverkusen-I. G. Werk, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application March 2, 1940, Serial No. 322,014. In Germany November 5, 1938 3 Claims.

from a cyclic organic base of the general formula wherein R stands for a bivalent hydrocarbon radical or the group consisting of ethylene, phenylene and naphthylene and X stands for a substituent of the group consisting of hydrogen, methyl, amino, methylimino, phenylimino, tolylimino and cyclohexylimino.

These salts are stated to be insoluble or difficultly soluble in water but solublein alcohol, acetone. benzyl alcohol, butanol, cyclohexanone or cyclohexanol.

The present invention is based upon the discovery that amines of the following constitution N.Cli

wherein R stands for a member of the group consisting of hydrogen and alkyl and R1 and R2 each stand for a member of the group consisting of alkyl and cycloalkyl,

the number of the carbon atoms present in the radicals defined by R, R1, R2 being at least 8, of converted into salts with organic compounds containing at least one acid salt forming group, impart to the latter a much better solubility in organic solvent than could be achieved by means of previously used amines. In consequence thereof. such salts are capable of yielding relatively highly concentrated solutions in organic solvents and can be employed for other applications than the hitherto known salts of the character described. The alkyl groups defined by the symbols R, R1 and R2 may bear various 'substituents without departing from the scope of our invention. Amines of the type defined by the above formula can be prepared in various ways, for instance by causing ketones to react upon formamide or alkylated formamides. Reference is made in this connection to the co-pending application Ser. No. 299,522 to Richard Wegler,. now Patent No. 2,251,245 of July 29, 1941. Another method of preparing such amines consists in causing ketones to react upon ammonia or alkyl amines in the presence of hydrogen. In preparing aminesof the character described such mixtures of ketones are preferred as are obtainable in a manner known per se from mixtures of aliphatic carboxylic acids obtainable by the oxydation of par-. aflines. As organic compounds containing acid salt forming groups there are preferably employed sulphonic acids or carboxylic acids of various dyestufis such as those of the azo, an'thraquinone, triphenylmethane or phthalocyanine series. Moreover, there can be employed those dyestuffs of the character described containing heavy metals in complex combination such as chromium or copper. The term organic dyestuffs is not limited to those exerting an absorbing action within the visible part of the spectrum but in- I eludes also those absorbing for instance ultra violet rays, and also fluorescent compounds. Salts of the character described can be employed for the coloring of organic solvents and of lacquers and molded articles prepared from organic plastic materials such as cellulose esters and cellulose'ethers. Salts of fluorescent compounds are employed for instance for marking lubricating oils, benzenes and alcohols. Salts of compounds absorbing within the ultra violet part of the spectrum can also be employed in lacquers, coatings and the like.

As a matter of fact, our new salts also present valuble pigment dyestufis as they are insoluble or at least diflicultly soluble in water.

Such salts can be prepared by causing the free 4 sulphonic or carboxylic acids toreact upon the free amine in the presence of water or anorganic solvent. In case of working with water the re- Example 1 10 parts of the dyestuff obtainable by coupling the diazocompound of 3-chloro-2- toluidine with the pyrazolone of the 2-toluidine-5-sulphonic acid are dissolved in 200 parts of water. The solution is rendered slightly acid by means of acetic acid. Thereupon the dyestui! i precipitated by means of the calculated quantity of an aqueous acetic acid solution of the amines wherein the average number of the carbon atoms in R1+R:=14. The whole is stirred for some. time at room temperature. Thereupon the dyestuif is sucked oil. It is soluble in ether, alcohol, acetone, chloroform, benzene and nitrocellulose lacquers with a yellow coloration.'

Example 2 Example 3 10 parts of the dyestui! obtainable from the diazocompound of the p-aminoazobenzene and pnaphthol-3.6.8-trlsulphonic acid are dissolved in parts of water and precipitated by means of an aqueous aceticacid solution or the amine described in Example 1. With a scarlet red solution the dry dyestuif is easily soluble in alcohol, acetone, chloroform and nitrocellulose lacquers. Contrary thereto, the corresponding dyestui! from dicyclohexylamine is diflicultly soluble in acetone and nitrocellulose lacquers.

Example 4 5 parts of the dyestuif, obtainable by conpiing the diasocompound of the p-aminoazobenzene with p-naphthol-ela-disulphonic acid, are dissolved in 200 parts of water, the solution is rendered slightly acetic acid and, thereupon, the dyestuii' is precipitated by means of the calculated amount of the amine of Example 1. With a clear red color the isolated dyestufi is easily soluble in alcohol, chloroform, benzene, acetone, nitrocellulose and butylacetate lacquers.

, Example 5 '5 parts of the dyestui! of Example 4 are dissolved in 200 parts of water and precipitated in an aqueous acetic acid solution with the. amine of the following constitution R1 OH.CHQ.CHl-NHC wherein the average number of the carbon atoms in R1+Rz=14. With red color the dyestui'f is easily soluble in acetone, alcohol, chloroform, benzene, nitrocellulose and butylacetate lacquers.

Example 6 10 parts 01 sodium pyrentetrasulphonic acid are dissolved in 100 parts of water and the solution is rendered slightly acetic acid. The sulphonic acid is precipitated by means of an aqueous acetic acid solution of the amine of Example 1. The resulting colorless salt solidifies on stirring. It is easily soluble in alcohol and chloroform.

' Example 7 30 parts of sodium pyrene-3-sulphonate are dissolved in 1500 parts of water and rendered slightly acetic acid. To the solution there are slowly added 20 parts of the amine of Example 1 dissolved in parts of an aqueous acetic acid. The salt of the pyrene sulphonic acid precipitates. It is sucked on and washed with water. After drying it represents a white powder which is easily soluble in alcohol, acetone, benzene and chloroform. It can be used in admixture with pyrene derivatives. as an agent absorbing ultraviolet rays for lacquers.

Example 8 10 parts of the dyestui'! obtainable by couplin the diazonium compound of the l-amino-B-nitrop-naphthol-d-sulphonic acid with p-naphthol and subjecting the dyestufl thus formed to an aftertreatment by means of chromium com pounds are dissolved in 100 parts of water and rendered acetic acid. Thereupon there are added thereto at room temperature so much of an acetic acid solution of the amine of Example 1 that the dye'stuff is completely precipitated. It is sucked oil and dried by exposure to the air. The dyestui! is easily soluble in acetone, alcohol and chloroform. It represents a black dyestufl suitable for coloring nitrocellulose lacquers.

Example 9 Sparta of the sulphonated oxazine dyestuii obtainable by condensing 2 mols of a-aminocarbazol with 1 mol of chloranil andsubsequently sulphonating the condensation product, are dissolved in 100 parts of water and precipitated in a slightly acetic acid solution with 3 parts of the amine of Example 1. The dyestufl is easily soluble in alcohol and nitrocellulose lacquers with a blueviolet color. I

Example 10 1 The copper phthalocyanine sulphonic acid chloride obtainable by heating copper phthalocyanine with the 15 fold quantity of chlorosulphonic acid to -150 C. is stirred at room temperature with an excess of the amine of Example 1. In the resulting product part of the sulphonic acid groups are converted into salts with the said amine, whereas the remaining part is present in form of the corresponding sulphonamides. It is easily soluble in chloroform, carbon disulphide and ether with a vivid bluish coloration.

Example 11 Example 12 5 parts of 1-amino-4-bromoanthraquinone-2- sulphonic acid are dissolved in 100 parts of wawashed with water.

ter. Thereupon 5.5 parts of the amine of Example 1 are added thereto. The whole is heated 5 parts of the chromium complex dyestufl obtainable by coupling the diazoniumcompound of the o-anisidine-4-diethylsulphonamide with pnaphthol-3.6-disulphonic acid followed by an aftertreatment with chromium salts are dissolved in 100 parts of water and rendered slightly acetic acid. The dyestufi is precipitated with 2.5 parts of the amine of Example 1 dissolved in parts of an aqueous acetic acid. The dyestufl is sucked on and dried. With red color it is easily soluble in alcohol, acetone, chloroform, nitrocellulose and butylacetat-lacquers.

Example 14 ,ylketone, ammonia and hydrogen. With a scarlet red coloration the dyestuif is easily soluble in alcohol, acetone, chloroform, ether, nitrocellulose and butylacetat-lacquers.

Example 15 A moist paste of the copperphthalocyaninesulphonic acid chloride prepared from 150 parts of copper phthalocyanine as described in Example 10 are suspended in 1200 parts of water. While stirring there are slowly added 165 parts of the amine corresponding to the formula NHr-Cfi wherein the average number of carbon atoms in R1 and Re=10 to 11. Subsequently 52 g. of soda dissolved in 250 com. of water are added. After 12 hours stirring the precipitated dyestufl is sucked oil, washed with 2% acetic acid and then After drying there is obtained a dyestuff in form of a blue powder which is easily soluble in alcohol, acetone and ethylacetat. The dyestui'i molecule contains besides sulphamidgroups at least one sulphonic acid group which is converted into a salt with the said amine.

Example 16 100 parts of the azodyestuif from p-aminoazobenzene and fi-naphthol-3.6.8-trisulphonic acid are suspended in 1000 parts of water and precipitated with a solution of 70 parts of the amine of Example 15 in 700 parts of water and '70 parts of glacial acetic acid. the solution of the amine being slowly added drop by drop. The precipitated dyestufi is sucked oiT, washed and dried. It represents a red powder which is excellently soluble in organic solvents.

Example 17 In Example 5 the amine of the formula stated therein is replaced by the tertiary amine obtainable by causing 8 mols of ethyleneoxide to react upon the-amine of the formula Bi HQN. Cg

(number of carbon atoms in R1 and R2 being 14) The resulting dyestuif is equally well soluble in organic solvents as that of Example 5.

Example 18 A 10 per cent acetic acid solution of an amine of the formula v (number of carbon atoms in R1 and B: being about 10) is added drop by drop intoan aqueous suspension of the azodyestufi' from diazotized anthranilic acid and 1-pheny1-3-methyl-5-pyrazolone until the dyestufl is completely precipitated. It represents a yellowish powder being easily soluble in alcohol, acetone, benzene and esters.

We claim: p

1. Salts formed from an organic dyestuff containing at least one acid salt-forming group and from an isoalkylamine of the following constitution wherein R stands for a member of the group consisting of hydrogen and alkyl, and R1 and R: each stand for a member of the group consisting of alkyl and cycloalkyl, the number of the carbon atoms present in the radicals defined by R, R1 and R2 being at least 8, said salts being insoluble or difllcultly soluble in water, but soluble in organic solvents.

' 2. Salts formed from an organic dyestuff containing at least one acid salt-forming group and selected from the group consisting of dyestuils of the azo, anthraquinone, triphenylmethane and phthalocyanlne series, and from an isoalkylamine of the following constitution:

wherein R stands for a member of the group consisting of hydrogen and alkyl, and R1 and R: each stands for a member of the group consisting of alkyl and cycloalkyl, the number of the carbon atoms present in the radicals defined by R. R1 and R2 being at least 8. said salts being insoluble or diflicultly soluble in water, but soluble in organic solvents. v 3. Salts formed from an organic dyestuff containing at least one acid salt-forming group, and from an isoalkylamine of the following constitution 2 the number ofthe carbon atoms contained in R1 and R2 being 14.

' FRIEDRICH NADLER.

RICHARD WEGLER. O'I'I'O BAYER. 

